Utilizing Hydrocarbon Containing Unsaturation Not Part Of Benzene Ring Patents (Class 502/108)
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Patent number: 6060416Abstract: A high-performance prepolymerized solid catalyst is prepared by polymerizing an olefin onto an olefin polymerization catalyst in a heterogeneous system under irradiation with an elastic wave, wherein the olefin is prepolymerized in an amount of not less than 0.1 g based on 1 mmol of a transition metal contained in the olefin polymerization catalyst. The elastic wave is preferably an ultrasonic wave. In a process for heterogeneous polymerization of an olefin, an olefin is subjected to slurry polymerization or gas phase polymerization in the presence of the prepolymerized solid catalyst. In a process for heterogeneous polymerization of an olefin, an olefin may be polymerized onto the olefin polymerization catalyst in a heterogeneous system under irradiation with an elastic wave to prepare polyolefin. Therefore, the heterogeneous polymerization of an olefin can be stably conducted and polyolefins of uniform property and high quality can be obtained.Type: GrantFiled: November 20, 1998Date of Patent: May 9, 2000Assignee: Mitsui ChemicalsInventors: Atsuo Kobata, Tetsuhiro Matsumoto
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Patent number: 5985783Abstract: A prepolymerized olefin polymerization catalyst, its prepration, and use are disclosed. The catalyst is prepared by contacting a solid particulate transition metal-containing olefin polymerization catalyst with an olefin in a confined zone under suitable conditions wherein the prepolymerization is conducted under conditions such that the olefin is added to the confined zone at a rate such that the pressure in the confined zone increases no more than about 0.5 psig/sec. during the olefin addition.Type: GrantFiled: May 27, 1993Date of Patent: November 16, 1999Assignee: Phillips Petroleum CompanyInventor: Kent E. Mitchell
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Patent number: 5958820Abstract: A process for polymerizing a gaseous conjugated diene by bringing it in contact with a catalyst consisting of a rare earth allyl compound, an organic aluminum compound, an inorganic support and optionally, the same or a different conjugated diene. The resulting polymers possess elevated proportions of cis-1,4 units.Type: GrantFiled: October 2, 1997Date of Patent: September 28, 1999Assignee: Bayer AGInventors: Rudolf Taube, Steffen Maiwald, Thomas Ruhmer, Heike Windisch, Jurgen Giesemann, Gerd Sylvester
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Patent number: 5939345Abstract: A high-performance prepolymerized solid catalyst is prepared by polymerizing an olefin onto an olefin polymerization catalyst in a heterogeneous system under irradiation with an elastic wave, wherein the olefin is prepolymerized in an amount of not less than 0.1 g based on 1 mmol of a transition metal contained in the olefin polymerization catalyst. The elastic wave is preferably an ultrasonic wave.Type: GrantFiled: August 26, 1997Date of Patent: August 17, 1999Assignee: Mitsui Chemicals, Inc.Inventors: Atsuo Kobata, Tetsuhiro Matsumoto
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Patent number: 5936049Abstract: Disclosed is a process for preparing a solid titanium catalyst component, comprising contacting (a) a liquid magnesium compound, (b) a liquid titanium compound, (c) an electron donor and (d) a solid divalent metallic halide. In this process, the solid divalent metallic halide is one having a crystalline structure of the cadmium chloride type. The contact of the component (a) with the component (b) is preferably carried out in the presence of the solid divalent metallic halide (d). According to this process, there can be obtained a solid titanium catalyst component capable of polymerizing olefins with an extremely high activity and capable of producing polyolefins of high stereoregularity when .alpha.-olefins of 3 or more carbon atoms are polymerized.Type: GrantFiled: April 7, 1997Date of Patent: August 10, 1999Assignee: Mitsui Chemicals, Inc.Inventors: Shinichi Kojoh, Masao Nakano
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Patent number: 5919877Abstract: Process for the in situ polymerization of ethylene with C.sub.3 -C.sub.10 alpha-olefins in suspension of liquid monomer in the presence of a catalyst containing Vanadium obtained by the precipitation, in an atmosphere of ethylene or alpha-olefins, of:a) a compound of Vanadium in the oxidation state of 3 to 5, withb) a basically hydrocarbon solution of a compound selected from those having general formula R.sub.n AlX.sub.m wherein R is a C.sub.1 -C.sub.20 alkyl radical, X is a halogen, m+n=3, n is an integer from 0 to 2.Type: GrantFiled: September 30, 1997Date of Patent: July 6, 1999Assignee: Enichem Elastomeri S.r l.Inventor: Tiziano Tanaglia
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Patent number: 5880056Abstract: Disclosed is an olefin polymerization catalyst comprising (A) a transition metal compound represented by the formula (I) R.sup.1 R.sup.2 MX.sub.2 (wherein M is a transition metal atom, R.sup.1 and R.sup.2 are each a cycloalkadienyl group having an aryl group and a saturated hydrocarbon group as substituents, and X is a halogen atom or the like) and (B) at least one compound selected from (b1) an organoaluminum oxy-compound, (b2) an ionized ionic compound and (b3) an organoaluminum compound. Also disclosed is a process for olefin polymerization comprising polymerizing an olefin in the presence of the above-mentioned catalyst. According to the present invention, an olefin copolymer having a crystallization temperature and a melting point both lower than those of the conventional copolymers can be prepared in the case of that the feeding amount of comonomer is smaller than those conventionally used.Type: GrantFiled: October 20, 1997Date of Patent: March 9, 1999Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Masaaki Ohgizawa
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Patent number: 5877109Abstract: Catalysts comprisingA) a rare earth alkoxide, a rare earth carboxylate and/or a rare earth coordination compound with diketones,B) an alumoxane andC) an inert, particulate, inorganic solid with a specific surface area of greater than 10 m.sup.2 /g and a pore volume of 0.3 to 15 ml/gare excellently suited to the polymerisation of conjugated dienes, in particular butadiene, in the gas phase.Type: GrantFiled: November 10, 1997Date of Patent: March 2, 1999Assignee: Bayer AGInventors: Karl-Heinz Reichert, Peter Marquardt, Christopher Eberstein, Birgit Garmatter, Gerd Sylvester
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Patent number: 5863853Abstract: This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst system of the invention provides for a supported bulky ligand transition metal catalyst system which when utilized in a polymerization process substantially reduces the reactor fouling and sheeting particularly in a gas phase polymerization process.Type: GrantFiled: February 24, 1997Date of Patent: January 26, 1999Assignee: Exxon Chemical Patents, Inc.Inventors: George Alan Vaughan, Anthony Nicholas Speca, Patrick Brant, Jo Ann Marie Canich
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Patent number: 5861352Abstract: A solid catalyst component for the polymerization and copolymerization of ethylene and alpha- olefins, containing a metallocene supported on an inorganic solid carrier constituted by a porous silicon oxide, the supported metallocene having the formula (I): ##STR1## wherein M is a group of metal, R' and R" are dialkylamide groups, R'" has the same definition as R' or is a cyclopentadienyl consisting ligand, and A is an anion containing an .eta..sup.5 -cyclopentadienyl ring coordinated to metal M, and wherein a carbon atom of the .eta..sup.5 -cyclopentadienyl ring of anion A is covalently bonded to the surface of the porous inorganic solid carrier.Type: GrantFiled: January 30, 1996Date of Patent: January 19, 1999Assignee: Enichem S.p.A.Inventors: Liliana Gila, Antonio Proto, Evelina Ballato, Diego Vigliarolo, Gabriele Lugli
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Preparation of supported auxiliary catalysts at elevated temperature and pressure in a closed vessel
Patent number: 5856255Abstract: A slurry is formed from an auxiliary catalyst (e.g., an aluminoxane or organoboron compound), a porous inorganic oxide carrier, and an inert organic solvent. The slurry is enclosed in a closed vessel and the temperature and pressure of the enclosed slurry are increased to a temperature of from about 80.degree. C. to 250.degree. C. and a pressure of from about 5 to 500 psig such that a supported composition is produced in the vessel. After opening the closed vessel, the supported composition and the solvent are separated from each other.Type: GrantFiled: January 22, 1996Date of Patent: January 5, 1999Assignee: Albemarle CorporationInventors: Niomi L. Krzystowczyk, Steven P. Diefenbach, John Y. Lee -
Patent number: 5856258Abstract: The subject invention involves a method of preparing and the constrained geometry catalyst thereby prepared of the general formula Ar'R4(O)Ar"R'.sub.4 M(CH.sub.2 Ph).sub.2 where Ar' is a phenyl or naphthyl group; Ar" is a cyclopentadienyl or indenyl group, R and R' are H or alkyl substituents (C.ltoreq.10) and M is Ti, Zr or Hf. The synthetic method involves a simple alkane elimination approach which permits a "one-pot" procedure. The catalyst, when combined with a cocatalyst such as Pb.sub.3 C.sup.+ B(Ar.sub.3.sup.F).sub.4 BAr.sub.3.sup.F or methyl alumoxane where Ar.sup.F is a fluoroaryl group, is an effective catalyst for the polymerization of .alpha.-olefins such as ethylene, propylene and styrene.Type: GrantFiled: October 15, 1997Date of Patent: January 5, 1999Assignee: Northwestern UniversityInventors: Tobin J. Marks, You-Xian Chen
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Patent number: 5852141Abstract: The present invention relates to a prepolymer for the polymerization of olefins, the said prepolymer achieving a combination of a number of solid catalytic components for the polymerization of olefins. The combination of catalytic components makes it possible to combine two properties within the same polymer, one of the properties being contributed by one of the catalytic components and the other property being contributed by the other catalytic component.Type: GrantFiled: September 17, 1996Date of Patent: December 22, 1998Assignee: Elf Atochem S.A.Inventor: Jean Malinge
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Patent number: 5824618Abstract: A catalyst component is disclosed for use in the homo- or copolymerization of olefinic hydrocarbons. The catalyst component is comprised of a first compound of the formula M.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q, M.sup.1 being titanium a second compound of the formula M.sup.2 (OR.sup.3).sub.m R.sup.4.sub.n X.sup.2.sub.z-m-n, with M.sup.2 being a metal of Groups Ia-IIIa or IIb of the Periodic Table, and a third compound which is an organocyclic compound having two or more conjugated double bonds. A process is also disclosed for the production of hydrocarbon polymers in which the above catalyst component is combined with a modified organoaluminum compound to form a catalyst composition capable of providing controlled molecular weight, wide distribution thereof and other desirable qualities in the polymer product.Type: GrantFiled: June 6, 1995Date of Patent: October 20, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Yoshio Tajima, Naoki Kataoka, Yosuke Numao, Takashi Seki, Kazuo Matsuura
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Patent number: 5814575Abstract: Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support, with a metal alkyl and an unsaturated hydrocarbon, to trimerize, oligomerize, and/or polymerize olefins.Type: GrantFiled: June 7, 1995Date of Patent: September 29, 1998Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman
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Patent number: 5786291Abstract: This invention relates to supported metallocene catalyst systems and to methods for their production and use. Specifically, this invention relates to supported catalyst systems having unique, predetermined properties resulting from the designed distribution of catalyst components within and upon porous support particles. The designed distribution of catalyst components is obtained through sequential deposition of catalyst components with intervening removal of solvent.Type: GrantFiled: February 18, 1997Date of Patent: July 28, 1998Assignee: Exxon Chemical Patents, Inc.Inventors: Anthony N. Speca, Jeffrey L. Brinen, James J. McAlpin
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Patent number: 5783512Abstract: A non-supported solid catalyst comprising (a) an ionic compound comprising a.1) a cation and a.2) an anion having up to 100 nonhydrogen atoms and said anion containing at least one substituent comprising an active hydrogen moiety, (b) a transition metal compound, and (c) an organometal compound wherein the metal is selected from the Groups 1-14 of the Periodic Table of the Elements; a supported solid catalyst comprising (a), (b), (c), and (d) a support material, obtainable by combining components (a), (b), (c), and (d) in any order, and wherein during at least one step in the preparation of the solid catalyst, component (a) dissolved in a diluent in which (a) is soluble, is converted into solid form; a method for preparing the solid catalysts; and a process of polymerization using these solid catalysts.Type: GrantFiled: December 18, 1996Date of Patent: July 21, 1998Assignee: The Dow Chemical CompanyInventors: Grant B. Jacobsen, Theo J. P. Stevens, Pierre H. H. Loix
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Patent number: 5780562Abstract: A novel olefin polymerization catalyst is obtained by contacting the following components (1) to (5) with one another: (1) a compound represented by the general formula Me.sup.1 R.sup.1.sub.p (OR.sup.2).sub.q X.sup.1.sub.4-p-q, (2) a compound represented by the general formula Me.sup.2 R.sup.3.sub.m (OR.sup.4).sub.n X.sup.2.sub.z-m-n, (3) an organocyclic compound having conjugated double bonds; (4) a modified organoaluminum compound having Al--O--Al bond(s); and (5) a silicon oxide and/or an aluminum oxide both having characteristic average particle diameter, specific surface area, volume of pores ranging in pore radius from 18 to 1,000 Angstroms, apparent specific gravity not lower than 0.32, and proportion of 50 .mu.m or smaller particles.Type: GrantFiled: August 21, 1995Date of Patent: July 14, 1998Assignees: Nippon Oil Co., Ltd., Mizusawa IndustrialInventors: Hiroyuki Shimizu, Akira Sano, Kazuo Matsuura, Yuuji Washio
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Patent number: 5780688Abstract: The invention concerns a supported catalyst in the form of packing and constructed on an open-pore support material on whose external and internal surfaces a macro-porous ion exchange resin is mechanically and/or chemically affixed.Type: GrantFiled: April 5, 1996Date of Patent: July 14, 1998Assignee: Veba Oel AGInventors: Ulrich Hoffmann, Ulrich Kunz, Hartmut Bruderreck, Klaus Gottlieb, Kuno Schadlich, Stefan Becker
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Patent number: 5767032Abstract: Provided are heterogeneous catalysts for homo- and copolymerization of olefins as well as a method for preparing these catalysts, which comprise at least one metallocene compound of a Group 4A, 5A or 6A (Hubbard) transition metal on a solid inorganic support. The mtehod comprises the steps of vaporizing the metallocene compound, treating the support material with the vaporized metallocene compound at a temperature which is sufficiently high to keep the metallocene compound in the vaporous state, contacting the support material with an amount of the vaporized metallocene compound which is sufficient to allow for a reaction between the metallocene compound and at least a substantial part of the available surface sites capable of reacting therewith, removing the rest of the metallocene compound not bound to the support, and optionally treating the product thus obtained with an activating agent. The catalysts are active even if very low amounts of activator agents, such as alumoxane, are used.Type: GrantFiled: August 12, 1997Date of Patent: June 16, 1998Assignee: Borealis A/SInventors: Harri Hokkanen, Hilkka Knuuttila, Eeva-Liisa Lakomaa, Pekka Sormunen
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Patent number: 5756609Abstract: An olefin homogeneous polymerization catalyst demonstrating increased activity is formed from a cyclopentadienyl metallocene component, a salt of a compatible cation and a non-coordinating anion, and a C.sub.3 -C.sub.6 trialkylaluminum, preferably triisobutylaluminum. A homogeneous polymerization process comprises controlling polymerization activity with such catalyst by controlling the aluminum/metal (Al/M) molar ratio to a minimal level within the effective range of Al/M ratios.Type: GrantFiled: October 17, 1996Date of Patent: May 26, 1998Assignee: Amoco CorporationInventor: Steven A. Cohen
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Patent number: 5753577Abstract: A novel class of olefin polymerization catalyst system based on specific organo-transition metal compounds and which are effective for controlling in particular the width and mode of the molecular weight distribution of the resulting polyolefins, and processes of olefin polymerization using the novel catalyst systems are disclosed.Type: GrantFiled: February 21, 1997Date of Patent: May 19, 1998Assignee: Tosoh CorporationInventors: Satoshi Hamura, Toru Yoshida, Morihiko Sato
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Patent number: 5747595Abstract: A catalyst for the polymerization of olefines comprises a solid catalytic component obtained by pre-polymerizing propylene in the presence of (A) a solid component containing magnesium, titanium, halogen and an electron-donating compound, (B) an organoaluminum compound, and (C) an alkylalkoxysilane represented by the formula, R.sup.1 Si(OR.sup.2)(OCH.sub.3).sub.2, wherein R.sup.1 represents a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R.sup.2 represents a branched alkyl, alkenyl or alkinyl group having 3 to 6 carbon atoms; (B) an organoaluminum compound; and (D) an alkyltrialkoxysilane represented by the formula, R.sup.3 Si(OR.sup.4).sub.2 (OCH.sub.3), wherein R.sup.3 represents a linear alkyl group having 3 to 6 carbon atoms, and R.sup.4 represents a branched alkyl, alkenyl or alkinyl group having 3 to 5 carbon atoms.Type: GrantFiled: March 27, 1996Date of Patent: May 5, 1998Assignee: Tonen CorporationInventors: Toshiya Saito, Takayuki Taki, Masashi Nakajima, Kunihiko Imanishi, Masahide Murata, Hiroyuki Ozaki, Kazukiyo Aiba, Masatoshi Ookura, Satoshi Ueki
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Patent number: 5744414Abstract: The present invention relates to a process for the preparation of a solid catalytic component of a catalyst of Ziegler-Natta type, comprising contacting (i) at least one compound (A) of a transition metal (TM) with (ii) a solid product (B) comprising a magnesium compound and having a reducing power for the transition metal (TM), in the presence of (iii) at least one olefin under conditions such that the olefin at least partially polymerizes during the contacting. The solid catalytic component is particularly useful for producing ethylene (co-)polymers in a gas phase process and for improving the statistical distribution of the comonomer in the copolymer structure.Type: GrantFiled: June 28, 1994Date of Patent: April 28, 1998Assignee: BP Chemicals LimitedInventor: Charles Jenny
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Patent number: 5733989Abstract: The present invention concerns prepolymerized catalyst composition for polymerization of .alpha.-olefins, a process for the preparation thereof and a process for polymerization of .alpha.-olefins. According to the polymerization process a procatalyst composition containing a transition metal is prepolymerized with a monomer in order to produce a prepolymerized Ziegler-Natta type catalyst composition and said catalyst composition is contacted with an alpha-olefin monomer, in particular with ethylene or propylene, for preparing a polymer. According to the invention the procatalyst composition is preferably prepolymerized in a medium which is inert to the catalyst components, the viscosity of the medium being so high that the catalyst does not substantially settle in this medium. Because the catalyst composition according to the invention does not have to be dried before being fed into the medium, its activity is high before and during polymerization.Type: GrantFiled: March 27, 1997Date of Patent: March 31, 1998Assignee: Borealis A/SInventors: Ismo Pentti, Pauli Leskinen
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Patent number: 5726264Abstract: A process to produce an ethylene-bridged-metallocene-transition-metal compound that has an omega-alkenyl substitution on said ethylene bridge is provided. Said process comprises: contacting a diolefin compound with a peracid compound to form an omega-alkenyl oxirane compound; contacting said omega-alkenyl oxirane compound with an organometal compound to form an organo-omega-alkenyl-alcohol compound; contacting said organo-omega-alkenyl-alcohol compound with an organosulfur compound to form an organo-omega-alkenyl-organosulfur ester compound; contacting said organo-omega-alkenyl-organosulfur ester compound with an organometal to form an orgaomega-alkenyl-organo compound; contacting said organo-omega-alkenyl-organo compound with a transition metal compound to form a organo-omega-alkenyl-organo-transition compound. Additionally, processes to polymerize olefins using these compounds is provided.Type: GrantFiled: June 14, 1996Date of Patent: March 10, 1998Assignee: Phillips Petroleum CompanyInventors: Michael Jung, Helmut G. Alt, M. Bruce Welch
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Patent number: 5705578Abstract: Methods are disclosed for preparing a highly active solid metallocene-containing catalyst system and its use in the polymerization of olefins. The solid catalyst system is prepared by combining an aluminoxane with a metallocene having a substituent which has internal alkynyl unsaturation in a suitable liquid to form a liquid catalyst system, conducting prepolymerization of an olefin in the liquid catalyst system, and separating the resulting solid metallocene-containing catalyst system from the last reaction product mixture. Also polymerization of olefins using the inventive solid catalyst system is disclosed.Type: GrantFiled: May 4, 1995Date of Patent: January 6, 1998Assignee: Phillips Petroleum CompanyInventors: Bernd Peifer, Helmut G. Alt, M. Bruce Welch
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Patent number: 5688734Abstract: The invention relates to a supported, prepolymerized metallocene catalyst system as well as its production and use in olefin polymerization. The method for producing the prepolymerized catalyst system involves prepolymerizing a metallocene catalyst system containing a volume of solution that is the equivalent of or less than the total pore volume of the supported catalyst system.Type: GrantFiled: September 19, 1996Date of Patent: November 18, 1997Assignees: Exxon Chemical Patents Inc., Hoechst AktiengesellschaftInventors: Anthony Nicholas Speca, Kelly Tormaschy
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Patent number: 5670589Abstract: In accordance with the present invention, there is provided an organoaluminoxy product prepared by the process comprising reacting an organoaluminoxane with an ene-ol compound. In another embodiment, the organoaluminoxane can be prepared in situ by the process comprising reacting a hydrocarbylaluminum compound, water, and the ene-ol compound. Further there is provided olefin polymerization catalyst systems comprising the organoaluminoxy product and at least one transition metal-containing catalyst. Optionally, the catalyst system is prepolymerized in the presence of at least one olefin to form a prepolymerized catalyst system. Still further there is provided processes for the polymerization of olefins using the catalyst systems.Type: GrantFiled: February 8, 1995Date of Patent: September 23, 1997Assignee: Phillips Petroleum CompanyInventors: Rolf L. Geerts, M. Bruce Welch, Syriac J. Palackal, Helmut G. Alt, Bernd Peifer, Harold R. Deck
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Patent number: 5661095Abstract: A catalyst component useful in the polymerization of olefins which includes a support formed of a copolymer of an olefin and a silane monomer having at least one unsaturated hydrocaryl substitutent. A process for making the catalyst component as well as a catalyst composition which includes the catalyst component is also set forth.Type: GrantFiled: June 6, 1995Date of Patent: August 26, 1997Assignee: Quantum Chemical CorporationInventors: Craig C. Meverden, Emory A. Ford
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Patent number: 5654248Abstract: A prepolymerized solid catalyst for gaseous phase or slurry polymerization of alpha olefins is disclosed. The catalyst comprises a porous carrier having a particle size of 20 to 200 microns onto which has been deposited an aluminoxane and a transition metal compound having at least one cycloalkadienyl group, the transition metal being from group 4 of the Periodic Table. The transition metal is present in an amount of 0.003 to 3 mmol/gm of carrier, and the aluminum to transition metal atomic ratio is from 15 to 1000. This catalyst is then prepolymerized with 0.2 to 30 gm of an alpha olefin per gram of catalyst to form the final prepolymerized solid catalyst having an intrinsic viscosity of 0.2 to 20 dl/gm as measured in decalin at 135 deg C.Type: GrantFiled: May 2, 1995Date of Patent: August 5, 1997Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Akinori Toyota, Norio Kashiwa, Toshiyuki Tsutsui
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Patent number: 5650528Abstract: In accordance with the present invention there is provided a cyclopentadienyl-type ligand represented by the formula ZA, wherein Z is a cyclopentadienyl-type group, wherein A is --YPR.sub.2, --YNR.sub.2, or --NR.sub.2, wherein Y is an alkylene group containing 1 to 24 carbon atoms, wherein each R is individually selected from alkyl groups containing 1 to 20 carbon atoms. Another aspect of the invention is to provide a metallocene represented by the formula ZAMX.sub.3, wherein Z and A are as described above, M is a Group IVB or VB transition metal, and X is a halide. Other aspects of the present invention include catalyst systems comprising the metallocenes and an organoaluminoxane, processes for preparing the above defined ligands, metallocenes and catalyst systems, and polymerization processes employing the catalyst systems.Type: GrantFiled: May 19, 1995Date of Patent: July 22, 1997Assignee: Phillips Petroleum CompanyInventors: Krisztina Frey, Gabriele von Massow, Helmut G. Alt, M. Bruce Welch
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Patent number: 5643845Abstract: A catalyst component is disclosed for use in the homo- or copolymerization of olefinic hydrocarbons. The catalyst component is comprised of a first compound of the formula Me.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q and a second compound which is an organocyclic compound having two or more conjugated double bonds. A process is also disclosed for the production of hydrocarbon polymers in which the above catalyst component is combined with a modified or organoaluminum compound to form a catalyst composition capable of providing high molecular weight, wide distribution thereof and other desirable qualities in the polymer product.Type: GrantFiled: November 4, 1994Date of Patent: July 1, 1997Assignee: Nippon Oil Co., Ltd.Inventors: Yoshio Tajima, Naoki Kataoka, Yosuke Numao, Takashi Seki, Kazuo Matsuura
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Patent number: 5635437Abstract: This invention is generally directed toward a method for producing metallocene catalyst systems. Specifically, the method involves removing solid impurities from a solution of activated metallocene wherein activation has the effect of solubilizing the metallocene but not the impurities. The resulting catalyst system is higher in activity and produces polymer having excellent particle morphology with little or no reactor fouling.Type: GrantFiled: July 28, 1995Date of Patent: June 3, 1997Assignees: Exxon Chemicals Patents, Inc., Hoechst AktiengesellschaftInventors: Terry J. Burkhardt, William B. Brandley
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Patent number: 5554704Abstract: The invention relates to a novel process for producing a supported metallocene catalyst system useful for the polymerization and/or copolymerization of olefins, alpha-olefins, and/or diolefins which results in a catalyst product which during polymerization, produces minimal to no reactor fouling and polymer of controlled morphology. The invention is particularly useful for but not limited to polymerizing propylene or copolymerizing propylene with olefins having two or more carbon atoms. The novel support technique described herein results in a catalyst which will obtain polymer product having controlled, uniform particle size, narrow molecular weight distribution, high bulk density and depending upon the metallocene employed and monomers polymerized, stereoregularity.Type: GrantFiled: July 1, 1994Date of Patent: September 10, 1996Assignee: Exxon Chemical Patents, Inc.Inventors: Terry J. Burkhardt, Masahide Murata, William B. Brandley
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Patent number: 5494871Abstract: A stable, long-lived catalyst composition, well suited for the polymerization of olefins, e.g., of ethylene, comprises intimate admixture of particulates of an olefin prepolymer and a catalytically effective amount of particles of a metallic olefin polymerization catalyst, such olefin prepolymer particulates having a particle size distribution narrower than the particle size distribution of the metallic catalyst particles.Type: GrantFiled: February 3, 1995Date of Patent: February 27, 1996Assignee: Elf Atochem S.A.Inventors: Claude Brun, Michel Avaro
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Patent number: 5468703Abstract: Disclosed is a titanium catalyst component for ethylene polymerization obtained by contacting [A] a solid magnesium aluminum complex containing magnesium, halogen, aluminum and an alkoxy group and/or alcohol having at least 6 carbon atoms, with [B] a tetravalent titanium compound. The solid magnesium aluminum complex [A] is obtained by contacting (a-1) a magnesium solution formed from a halogen-containing magnesium compound, an alcohol having at least 6 carbon atoms and a hydrocarbon solvent, with (a-2) an organoaluminum compound. Also disclosed is a process for ethylene polymerization comprising polymerizing ethylene or copolymerizing ethylene with an .alpha.-olefin having 3 to 20 carbon atoms in the presence of a catalyst for ethylene polymerization comprising [I] the above-mentioned titanium catalyst component for ethylene polymerization and [II] an organoaluminum compound catalyst component.Type: GrantFiled: October 4, 1993Date of Patent: November 21, 1995Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Tsuneo Yashiki
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Patent number: 5432139Abstract: Processes for the formulation of Ziegler-type catalysts from a transition metal component, an electron donor and a co-catalyst which are sequentially mixed together. The co-catalyst is initially contacted with either of the transition metal catalyst or the electron donor for a first contact time of 5-120 seconds. This mixture is then contacted with the remainder of the electron donor or transition metal component for a second contact time of less and 110 seconds. The three component system is then used in olefin polymerization. The olefin contacting step can involve an initial pre-polymerization reaction. A specific order of addition involves mixture of the transition metal component and the co-catalyst component for a contact time of 5-120 seconds followed by contact with an electron donor component for no more than 30 seconds. Another order of addition involves initially contacting the electron donor with the co-catalyst.Type: GrantFiled: March 4, 1992Date of Patent: July 11, 1995Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David J. Rauscher, Shabbir A. Malbari
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Patent number: 5416179Abstract: A process for the polymerization of mono-1-olefins employing a catalyst composition comprising a metallocene compound and isobutene. The catalyst composition exhibits improved productivity. In a preferred embodiment an aluminoxane is employed as a cocatalyst.Type: GrantFiled: March 16, 1994Date of Patent: May 16, 1995Assignee: Phillips Petroleum CompanyInventors: M. Bruce Welch, Paul Barbee
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Patent number: 5409874Abstract: The catalyst for olefin polymerization of the present invention contains R.sup.1.sub.k R.sup.2.sub.l R.sup.3.sub.m M(SO.sub.3 R.sup.4) (M=Zr, Ti or Hf; R.sup.1-3 =a group having a cyclopentadienyl skeleton) as a catalyst component of a transition metal compound. According to the catalyst of the invention, an olefin polymer having excellent particle properties can be prepared with high polymerization activities, and further a copolymer having a narrow composition distribution can be prepared when two or more monomers are copolymerized. Of the above-mentioned transition metal compounds, a compound represented by the following formula is a novel compound unknown so far and shows excellent catalytic properties. ##STR1## (Cp=a group having a cyclopentadienyl skeleton, X=SO.sub.3 R, a halogen atom, R, OR, NR.sub.n, S(O).sub.q R, SiR.sub.3 or P(O).sub.q R.sub.Type: GrantFiled: June 19, 1992Date of Patent: April 25, 1995Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Junichi Imuta, Junji Saito, Takashi Ueda, Teruaki Mukaiyama
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Patent number: 5405816Abstract: Pure syndiotactic 1,2-polybutadiene is a thermoplastic resin which has double bonds attached in an alternating fashion to its polymeric backbone. Films, fibers and molded articles can be made utilizing syndiotactic 1,2-polybutadiene. It can also be blended into rubbers and cocured therewith. Syndiotactic 1,2-polybutadiene can be made by solution, emulsion or suspension polymerization. It typically has a melting point which is within the range of about 195.degree. C. to about 215.degree. C. However, it is often desirable for the syndiotactic 1,2-polybutadiene to have a melting point of less than about 195.degree. C. This invention discloses a process for preparing syndiotactic 1,2-polybutadiene having a melting point of less than about 195.degree. C.Type: GrantFiled: September 22, 1993Date of Patent: April 11, 1995Assignee: The Goodyear Tire & Rubber CompanyInventor: Gary L. Burroway
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Patent number: 5399539Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.Type: GrantFiled: June 24, 1994Date of Patent: March 21, 1995Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn
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Patent number: 5399638Abstract: The method of forming a catalytic component for use in the polymerization of ethylene or a copolymer of ethylene and a C.sub.3 to C.sub.12 alpha olefin in a gas-phase comprising impregnating a porous metal oxide support with at least one titanium compound, magnesium compound, and chlorine compound, and prepolymerizing ethylene or a copolymer of ethylene and a C.sub.3 to C.sub.12 alpha olefin, a least partially in suspension, in the presence of said porous metal oxide support and at least one alkylaluminum compound until a degree of prepolymerization is reached which is suitable for the subsequent gas-phase of fluidized bed polymerization, and the method of polymerizing olefins utilizing the catalysts formed by the prepolymerization.Type: GrantFiled: January 10, 1992Date of Patent: March 21, 1995Assignee: AtochemInventors: Claude Brun, Auguste Cheux, Eric Barthel
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Patent number: 5387567Abstract: A catalyst component is disclosed for use in the homo-or copolymerization of olefinic hydrocarbons. The catalyst component is comprised of a first compound of the formula Me.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q and a second compound which is an organocyclic compound having two or more conjugated double bonds. A process is also disclosed for the production of hydrocarbon polymers in which the above catalyst component is combined with a modified organoaluminum compound to form a catalyst composition capable of providing high molecular weight, wide distribution thereof and other desirable qualities in the polymer product.Type: GrantFiled: June 26, 1992Date of Patent: February 7, 1995Assignee: Nippon Oil Co., Ltd.Inventors: Yoshio Tajima, Naoki Kataoka, Yosuke Numao, Takashi Seki, Kazuo Matsuura
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Patent number: 5378672Abstract: A system for combining the components of a multi-component catalyst system comprising at least four chambers with flow passageway means connecting the chambers in series. The catalyst components can include a transition metal, an electron donor and a co-catalyst, which are sequentially mixed together in the course of formulating a Ziegler-type system to be charged to an olefin polymerization reactor. The passages between the second and third chambers have valves. Each of the second and fourth chambers is provided with an inlet opening separate from the interconnecting flow passages and a vent opening separate from the inlet openings and the interconnecting flow passages. The chamber also has an outlet opening. This system also has flushing inlet passages for each of the four chambers which are connected to a manifold adapted to be connected to a source of nitrogen.Type: GrantFiled: March 4, 1992Date of Patent: January 3, 1995Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David J. Rauscher, Shabbir A. Malbari
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Patent number: 5376612Abstract: Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support, with a metal alkyl and an unsaturated hydrocarbon, to trimerize, oligomerize, and/or polymerize olefins.Type: GrantFiled: August 20, 1993Date of Patent: December 27, 1994Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman
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Patent number: 5374597Abstract: Catalysts useful in olefin polymerization are a mixture of (a) (i) one or more compounds Zn(X.sup.1).sub.2 and one or more compounds Al(R.sup.1).sub.3, or (ii) Zn(X.sup.1).sub.2.2Al(R.sup.1).sub.3, wherein X.sup.1 is halide and R.sup.1 is C.sub.1-12 hydrocarbyl; and (b) one or more of V(X.sup.2).sub.c (OR.sup.2).sub.b-c, VO(X.sup.3).sub.d (OR.sup.3).sub.3-d, or VO(X.sup.4).sub.2, wherein X.sup.2, X.sup.3 and X.sup.4 are halogen, R.sup.2 and R.sup.3 are C.sub.1-18 hydrocarbyl, b is 3-4, c is 0-b, and d is 0-3; and can contain (c) one or more of M(R.sup.5).sub.e (X.sup.5).sub.3-e, Al.sub.2 (R.sup.5).sub.3 (X.sup.5).sub.3 or Mg(R.sup.6).sub.f Y.sub.2-f, wherein X.sup.1 and X.sup.2 are halide, R.sup.1, R.sup.5, R.sup.6 and R.sup.9 are C.sub.1- 12 hydrocarbyl, M is Al or B, e is 0-3, Y is halide, O--(C.sub.1-12 hydrocarbyl) or N(SiR.sup.9.sub.3).sub.2, and f is 0-2.Type: GrantFiled: February 12, 1993Date of Patent: December 20, 1994Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5342907Abstract: A process comprising contacting a mixture comprising ethylene, propylene, and, optionally, a diene, in the gas phase, under polymerization conditions, with a catalyst system comprising:(a) a catalyst precursor, in independent or prepolymer form, consisting of vanadium (acetylacetonate).sub.3 ;(b) optionally, a support for said precursor;(c) a cocatalyst consisting essentially of (i) an alkylaluminum halide having the formula AlR.sub.(3-a) X.sub.a wherein each R is independently alkyl having 1 to 14 carbon atoms; each X is independently chlorine, bromine, or iodine; and a is 1 or 2, and (ii) optionally, a trialkylaluminum provided that the molar ratio of alkylaluminum halide to trialkylaluminum is at least about 1.Type: GrantFiled: June 28, 1993Date of Patent: August 30, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Kevin J. Cann, Fathi D. Hussein, Kiu H. Lee, Daniel P. Zilker, Jr., James W. Nicoletti, Xinlai Bai
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Patent number: 5340785Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.Type: GrantFiled: February 26, 1993Date of Patent: August 23, 1994Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn
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Patent number: RE35324Abstract: The present invention relates to a process for the polymerization of ethylene or copolymerization of ethylene and at least one other alpha-olefin, in the gas phase in a fluidized bed reactor, in the presence of a catalyst comprising chromium compounds associated with a granular support comprising a refractory oxide and activated by thermal treatment, which process is characterized in that the catalyst is used in the form of active particles of prepolymer, obtained by bringing the said catalyst in contact with ethylene, alone, or in a mixture with at least one higher alpha-olefin, in such a way that the prepolymer contains from 4.times.10.sup.-5 to 3 milligram atoms of chromium in the catalyst per gram.Type: GrantFiled: March 14, 1995Date of Patent: September 3, 1996Assignee: BP Chemicals LimitedInventors: Jean-Claude A. Bailly, John G. Speakman